Organic compositions containing amino-guanidine antioxidants

ABSTRACT

ORGANIC COMPOSITIONS ARE PROVIDED CONTAINING, AS IMPROVING AGENTS, COMPOUNDS SELECTED FROM THE GROUP CONSISTING OF KETIMINES OF AMINOGUANIDINE, ALDIMINES OF KETIMINES OF AMINOGUANIDINE AND ALDIMINES OF AMIDES OF AMINOGUANIDINES. THESE COMPOUNDS ACT AS ANTIOXIDANTS AND METAL DEACTIVATORS FOR FUEL OILS, LUBRICATING OILS AND GREASES.

United States Patent O 3,809,719 ORGANIC COMPOSITIONS CONTAINING AMINO- GUANIDINE ANTIOXIDANTS Harry J. Andress, Jr., Pitman, N.J., assignor to Mobil Oil Corporation No Drawing. Original application May 18, 1970, Ser. No. 38,500, now Patent No. 3,655,560, dated Apr. 11, 1972. Divided and this application May 19, 1971, Ser.

Int. Cl. C07c 129/12 US. Cl. 260-564 F 2 Claims ABSTRACT OF THE DISCLOSURE Organic compositions are provided containing, as improving agents, compounds selected from the group consisting of ketimines of aminoguanidine, aldimines of ketimines of aminoguanidine and aldimines of amides of aminoguanidines. These compounds act as antioxidants and metal deaetivators for fuel oils, lubricating oils and greases.

CROSS-REFERENCE TO RELATED APPLICATIONS This application is a division of my copending application Ser. No. 38,500, filed May 18, 1970, now US. Pat. 3,655,560, issued Apr. 11, 1972.

BACKGROUND OF THE INVENTION (1) Field of the invention This invention relates to organic compositions and, in one of its aspects, relates more particularly to improved organic compositions in the form of liquid and solid hydrocarbons which, when employed as fuel oils, normally cause gum formation upon combustion or, when in the form of lubricating oils or greases, are subject to oxidative deterioration. Still more particularly, in this aspect, the invention relates to improved organic compositions in the form of petroleum distillate hydrocarbon fuels, lubricating oils or greases which, in their uninhibited state, tend to result in the above-described deleterious conditions in the course of use or storage.

(2) Description of the prior art It is Well known that certain types of organic compositions in the form of liquid hydrocarbon fuels normally result in gum formation or cause screen clogging upon combustion. Furthermore, it is also known that organic compositions, when employed in the form of lubricating oils or greases containing such oils as vehicles, are subject to oxidative deterioration in the course of their functional environment, thus clearly indicating the necessity for incorporating into such organic compositions effective improving agents.

SUMMARY OF THE INVENTION It has now been found that the aforementioned gum formation or oxidative deterioration properties of organic compositions, particularly in the form of fuels and lubricants can be effectively overcome by incorporating therein small amounts of an additive agent selected from the group consisting of ketimines of aminoguanidine, aldimines of ketimines of aminoguanidine and aldimines of amides of aminoguanidine.

In general, the present invention, in its preferred applications, contemplates organic compositions of the above-described types which contain a small amount of the aforementioned aminoguanidine, usually from about 0.1 to about 200 pounds per thousand barrels, and preferably from about 1 to about 10 pounds per thousand barrels of the total weight of such compositions.

ice.

The organic compositions improved in accordance with the present invention may comprise any materials that are normally susceptible to the above-described screen clogging or oxidative deterioration characteristics. A field of specific applicability is the improvement of liquid hydrocarbons boiling from about 75 F. to about 1000 F. Of particular significance is the treatment of petroleum distillate fuel oils having an initial boiling point from about 75 F. to about 135 F. and an end boiling point from about 250 F. to about 750 F. It should be noted, in this respect, that the term distillate fuel oils is not intended to be restricted to straight-run distillate fractions. These distillate fuel oils can be straight-run distillate fuel oils, catalytically or thermally cracked (including hydrocracked) distillate fuel oils, or mixtures of straight-run distillate fuel oils, naphthas and the like, with cracked distillate stocks. Moreover, such fuel oils can be treated in accordance with well-known commercial methods, such as acid or caustic treatment, hydrogenation, solvent-refining, clay treatment and the like.

The distillate fuel oils are characterized by their rela tively low viscosity, pour point and the like. The principal property which characterizes these hydrocarbons, however, is their distillation range. As hereinbefore indicated, this range will lie between about 75 F. and about 750 F. Obviously, the distillation range of each individual fuel oil will cover a narrower boiling range, falling nevertheless within the above-specified limits. Likewise, each fuel oil will boil substantially, continuously throughout its distillation range.

Particularly contemplated among the fuel oils are Numbers 1, 2 and 3 fuel oils used in heating and as diesel fuel oils, gasoline and jet combustion fuels. The domestic fuel oils generally conform to the specifications set forth in ASTM Specification D396-48T. Specifications for diesel fuels are defined in ASTM Specification D975-48T. Typical jet fuels are defined in Military Specification MIL-F-5624B. In addition, as previously indicated, hydrocarbon lubricating oils of varying viscosity and pour points, falling both within the aforementioned range and as high as 1000 F. and higher may also be effectively treated through the use of thee aforementioned additive agents.

As previously indicated, the aforementioned additive agents of the present invention may also be incorporated as antioxidants in grease compositions. Such greases may comprise a combination of a Wide variety of lubricating vehicles and thickening or gelling agents. Thus greases in which the aforementioned additive agents are particularly effective, may comprise any of the conventional hydrocarbon oils of lubricating viscosity, as the oil vehicle, and may include mineral or synthetic lubricating oils, aliphatic phosphates, esters and di-esters, silicates, siloxanes and oxalkyl ethers and esters. Mineral lubricating oils, employed as the lubricating vehicle, may be of any suitable lubricating viscosity range from about 45 SSU at 100 F. to about 6000 SSU at 100 F., and, preferably, from about 50 to about 250 SSU at 210 F. These oils may have viscosity indexes varying from below 0 to about 100 or higher. Viscosity indexes from about to about are preferred. The average molecular weights of these oils may range from about 250 to about 800. The lubricating oil is employed in the grease composition in an amount sufiicient to constitute the balance of the total grease composition, after accounting for the desired quantity of the thickening agent, and other additive components to be included in the grease formulation.

or synthetic oils of lubricating viscosity. When high temperature stability is not a requirement of the finished grease, mineral oils having a viscosity of at least 40 SSU at 100 F., and particularly those falling within the range from about 60 SSU to about 6,000 SSU at 100 F., may be employed. In instances where synthetic vehicles are employed rather than mineral oils, or in combination therewith, as the lubricating vehicle, various compounds of this type may be successfully utilized. Typical synthetic vehicles include: polypropylene, polypropylene glycol, trimethylol propane esters, neopentyl and pentaerythritol esters, di(2-ethyl hexyl) sebacate, di(2-ethyl hexyl) adipate, di-butyl phthalate, fluorocarbons, silicate esters, silanes, esters of phosphorus-containing acids, liquid ureas, ferrocene derivatives, hydrogenated mineral oils, chaintype polyphenyls, siloxanes and silicones (polysiloxanes), alkyl-substituted diphenyl ethers typified by a butyl-substituted bis(p-phenoxy phenyl) ether, phenoxy phenylethers, etc.

The lubricating vehicles of the aforementioned improved greases of the present invention containing the above-described additive agents are combined with a grease-forming quantity of a thickening agent. For this purpose, a wide variety of materials may be employed. These thickening or gelling agents may include any of the conventional additive agents or soaps, which are dispersed in the lubricating vehicle in grease-forming quantities in such degree as to impart to the resulting grease composition the desired consistency. Other thickening agents that may be employed in the grease formulation may comprise the non-soap thickeners, such as surfacemodified clays and silicas, aryl ureas, calcium complexes and similar materials. In general, grease thickeners may be employed which do not melt and dissolve when used at the required temperature within a particular environment; however, in all other respects, any material which is normally employed for thickening or gelling hydrocarbon fluids for forming grease can be used in preparing the aforementioned improved grease in accordance with the present invention.

The novel improving agents of the present invention may be prepared, in general, by reacting an aminoguanidine salt with a ketone to produce the corresponding ketimine of aminoguanidine; or a ketimine of aminoguanidine thus produced may be further reacted with an aldehyde to produce the corresponding aldimine of the ketimine of aminoguanidine. Each of these reactions can be carried out at a temperature from about 100 C. to about 200 C. and in a mol ratio of 1:1. It is also within the scope of the invention to react an aminoguanidine salt, an organic acid and an aldehyde, at the above temperature range and in a mol ratio of 1:1:1, to produce the corresponding aldimine of the amide of aminoguanidine. For

the above described reactions, a wide variety of aminoguanidine salts, ketones, aldehydes, acids and derivatives thereof may be succesfully employed.

DESCRIPTION OF SPECIFIC EMBODIMENTS The following data and examples will serve to illustrate the preparation of the novel additive agents of the present invention and their eflicacy as improving agents in organic compositions. It will be understood, however, that it is not intended the invention be limited to the particular additive agents or the particular organic compositions containing these agents, as described. Various modifications of these agents and organic compositions can be employed and will readily be apparent to those skilled in the art.

EXAMPLE 1 Preparation of the methylcoco ketimine of aminoguanidine A mixture of 68 grams (0.5 mol) aminoguanidine bicarbonate, 110 grams (0.5 mol) methylcoco ketone and 100 grams of benzene diluent was refluxed to a tempera ture of about 175 C. over a pe iod O about 8 hours to of aminoguanidine.

produce the final product, viz. the methylcoco ketimine EXAMPLE 2 Preparation of the salicylaldimine of the methylcoco ketimine of aminoguanidine To 159 grams (0.5 mol) of the product prepared in accordance with Example 1 were added 61 grams (0.5 mol) salicylaldehyde and grams of toluene. The resulting mixture was stirred at a temperature of C. for a period of about 3 hours to produce the final product, viz. the salicylaldimine of the methylcoco ketimine of aminoguanidine.

EXAMPLE 3 Preparation of the salicylaldimine of methylnonyl ketimine of aminoguanidine A mixture of 136 grams (1.0 mol) aminoguanidine bicarbonate, 170 grams (1 mol) methylnonyl ketone and 100 grams of benzene as a diluent was refluxed to a temperature of about C. over a period of about 8 hours. The resulting mixture was then cooled to 90 C. and 122 grams (1 mol) salicylaldehyde and 200 grams toluene were added. The resulting mixturewas then refluxed to a temperature of about 177 C. over a 6 hour period to produce the final product, viz. the salicyaldimine of the methylnonyl ketimine of aminoguanidine.

EXAMPLE 4 Preparation of the salicylaldimine of phenylstearyl amide of aminoguanidine A mixture of 68 grams (0.5 mol) aminoguanidine bicarbonate, 100 grams (0.5 mol) phenylstearic acid and 100 grams benzene was refluxed to a temperature of about 177 C. over a period of about 8 hours. The resulting mixture was cooled to 80 C. and 61 grams (0.5 mol) salicylaldehyde and 100 grams toluene were added. The resulting mixture was then refluxed to a temperature of about 178 C. over a '6 hour period to produce the final product, viz. the salicylaldimine of phenylstearyl amide of aminoguanidine.

The novel ketimines of aminoguanidine, as illustrated by Example 1, have the following general structural formula:

in which R and R are each alkyl or aryl.

In Example 1, R is methyl and R is C -C with an average of C The aldimines of lketimines of aminoguanidines, as illustrated by Examples 2 and 3, have the following general structural formula:

in which R and R are each alkyl or aryl.

In Example 2, R is methyl and R is C -C with an average of C In Example 3, R is methyl and R is C The aldimines of amides of aminoguanidine, as illustrated by Example 4, have the following general structural formula:

in which R is carboxyl.

In Example 4, R is phenylstearyl.

The oxidation stability of a fuel in the form of gasoline, employing the novel aminoguanidine compounds of the present invention, was tested by the Induction Period Method, in accordance with ASTM Test D525. The inhibitor agents of the present invention, as set forth in Table I, below, were blended in a full boiling range catalytically cracked gasoline containing 3 cc. of uninhibited tetraethyl lead fluid per gallon within a 100400 F. boiling range.

lbsl/ 0.2 mg.ll.

1,000 No copper, copper, mg./ Compound bbls. mg./100 ml. 100 m1.

Base gasoline 0 6 Base gasoline plus- Ex. 1 10 8. 41.0 Ex. 2 3. 4 4. 0 Ex. 3--.- 10 3.5 3.3 Ex. 4 10 5.4 8. 4

The respective additives of the foregoing examples were next subjected to a standard gasoline storage test. This test was used to determine the quantity of gum increase in both a gasoline blend comprising the same base fuel as in Table I, supra, comprising 100% catalytically cracked components and containing 3 cc. tetraethyl lead per gallon within a l00400 F. boiling range, and the same gasoline blend containing, also, the additive compositions of the examples. After being maintained at 110 F. for a period of 16 weeks, the amount of gum increase was determined according to ASTM Test D381. The test results comparing the uninhibited gasolines and the same gasoline containing the additive agents of the examples are set forth in Table III.

TABLE III Gum Cone,

lbs./ 0.2 mg.ll. 1,000 No copper, copper, mgJ Compound bbls. mg./ ml. 100 ml.

Base gasoline 0 25. 5 36. 5

Base gasoline plus- Ex. 1.-- 10 18.0 28. 0 Ex. 2.-- 10 8. 2 12. 8 Ex. 3--. 10 7. 2 l0. 0 Ex. 4 1O 17. 5 26. 7

The oxidation and corrosion evaluation of the additive agents of the present invention with respect to lubricants, was next determined in accordance with Federal Test Method 53-08. In this test the inhibitors were blended in a base lubricant comprising the mixed caprylyl and pelargonyl esters of 2-methyl, 2-ethyl, 1,3-propanediol. The test was carried out at a temperature of 400 F. for a period of 72 hours. The results of this test are shown in the following Table IV.

From the foregoing comparative data, it will be apparent that the novel aminoguanidine compounds of the present invention are highly effective as antioxidants and metal deactivators for fuel oils and hydrocarbon lubricants. Although the present invention has been described with preferred embodiments, it will be understood that various modifications and adaptations thereof may be resorted to without departing from the spirit and scope of the invention and that the compositions therein disclosed may also contain other additives intended to enhance their properties.

I claim:

1. As a composition of matter, the salicylaldimine of the methylcoco ketimine of aminoguanidine.

2. As a composition of matter, the salicylaldimine of the methylnonyl ketimine of aminoguanidine.

References Cited UNITED STATES PATENTS 7/1944 Clarkson et a1. 260-564 F X 9/1960 Birtwell et a1. 260-564 F X 

